Gels comprising novel fluorinated and alkylated alditol derivatives

ABSTRACT

Plastic additives which are useful as nucleating agents and which are especially useful for improving the optical properties of polymeric materials are provided. More particularly, this invention relates to certain alkyl (or alkoxy) substituted fluoro-benzylidene sorbitol acetals and polymer compositions thereof which may be utilized within, as merely examples, food or cosmetic containers and packaging. These inventive fluorinated and alkylated benzylidene sorbitol acetals are also useful as gelling agents for water and organic solvents, particularly those used in the preparation of antiperspirant gel sticks.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of co-pending application Ser. No.09/816,965, filed on Mar. 23, 2001 allowed, which is acontinuation-in-part of application Ser. No. 09/653,935, filed on Sep.1, 2000, now U.S. Pat. No. 6,300,525. These parent applications areherein entirely incorporated by reference.

FIELD OF THE INVENTION

This invention relates to plastic additives which are useful asnucleating agents and which are especially useful for improving theoptical properties of polymeric materials. More particularly, thisinvention relates to certain alkyl (or alkoxy) substitutedfluoro-benzylidene sorbitol acetals and polymer compositions thereofwhich may be utilized within, as merely examples, food or cosmeticcontainers and packaging. These inventive fluorinated and alkylatedbenzylidene sorbitol acetals are also useful as gelling agents for waterand organic solvents, particularly those used in the preparation ofantiperspirant gel sticks.

BACKGROUND OF THE PRIOR ART

All U.S. Patents cited below are herein entirely incorporated byreference. Numerous attempts have been made to improve the clarity andphysical properties of polyolefins through the incorporation of certainkinds of additives. Certain applications require good clarity ortransparency characteristics. These include certain types of plasticplates, sheets, films, containers, and syringes that need to exhibitclarity primarily to facilitate identification of articles, etc.,stored, wrapped, and/or covered therewith. Such commercially availableplastic additives fall into two categories termed “melt sensitive” and“melt insensitive”. Melt sensitive additives possess melting pointsbelow or near the normal processing temperatures of polyolefin-basedresins and include dibenzylidene sorbitol (DBS) systems. Meltinsensitive additives do not melt at normal processing temperatures andinclude sodium benzoate and salts of organic phosphates as examples.

U.S. Pat. No 4,016,118 to Hamada, et al. teaches that a polyolefinplastic composition containing 0.1% to 0.7% dibenzylidene sorbitol (DBS)as an additive will show improved transparency and reduced moldingshrinkage over compositions containing a substituted benzoic acid salt.Additional advancements in sorbitol-based clarification technology havebeen driven by the need for improved transparency, reduction ofplate-out during processing, and improved organoleptic properties (e.g.,odor, taste, etc.). In order to overcome these deficiencies, manyderivatives of DBS in which the aromatic rings are substituted withvarious groups have been proposed.

Mahaffey, in U.S. Pat. No. 4,371,645 discloses a series of dibenzylidenesorbitols having the general formula:

wherein R, R₁, R₂, R₃, and R₄ are selected from hydrogen, lower alkyl,hydroxy, methoxy, mono- and di-alkylamino, amino, nitro, and halogen,with the proviso that at least one of R₁, R₂, R₃, and R₄ is chlorine orbromine. Effective concentrations of the disclosed substituted DBSderivatives range from 0.01 to about 2 percent of the total compositionby weight. Further improvements in transparency characteristics aredisclosed by Titus, et al. in U.S. Pat. No. 4,808,650. In this patentmono and disubstituted DBS derivatives having the formula:

in which R may be hydrogen or fluorine provide improved clarityapplications in polyolefins. Rekers, in U.S. Pat. No. 5,049,605discloses a series of dibenzylidene sorbitols having the generalformula:

in which R₁ and R₂ are independently selected from lower alkyl groupscontaining 1-4 carbons which together form a carbocyclic ring containingup to 5 carbon atoms. Also disclosed are polyolefin plastics containingthe above group of dibenzylidene sorbitols. Videau, in U.S. Pat. No.5,696,186 discloses substituted DBS derivatives with an alkyl group(methyl, ethyl, or the like) or halogen (fluorine, chlorine, or thelike) on the benzene rings for use as nucleation/clarification agents inpolyolefins.

Dibenzylidene sorbitol (DBS) is a well known gelling agent for a varietysolvent systems as disclosed in U.S. Pat. No. 4,154,816, Roehl et al.;U.S. Pat. No. 4,816,261, Luebbe et al.; and U.S. Pat. No. 4,743,444 toMcCall. U.S. Pat. No. 5,609,855 to Oh et al. and PCT Patent ApplicationWO/92/19221 to Juneja et al.; disclose that di(meta-fluorobenzylidene)sorbitol and di(meta-chlorobenzylidene) sorbitol are extremely useful asgelling agents in the preparation of antiperspirant gel sticks. Thesetwo respective DBS systems form effective hard gels and show improvedgel stability in the acidic environment of antiperspirant formulations.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention, a polyolefin plastic compositionhaving improved transparency is provided which comprises a polymerselected from aliphatic polyolefins and copolymers containing at leastone aliphatic olefin and one or more ethylenically unsaturatedcomonomers and at least one di-acetal of an alditol (such as sorbitol,xylitol, and ribitol), said di-acetal of the alditol having thestructure:

wherein R is independently selected from hydrogen, lower alkyl groupscontaining 1-4 carbon atoms, lower alkoxy groups, and fluorine; R₁, R₂,R₃, and R₄ are selected from lower alkyl groups containing 1-4 carbonatoms, lower alkoxy groups, chlorine, and fluorine; with the provisothat one and only one of R₁ and R₂ is fluorine and one and only one ofR₃ and R₄ is fluorine.

This invention also encompasses such specific compounds themselves, intheir broadest sense defined as benzylidene alditol acetals comprisingat least one substituted benzylidene component wherein said at least onesubstituted benzylidene component possesses at least one fluorinependant group and at least one other pendant group, wherein said atleast one other pendant group is not hydrogen, and wherein if said atleast one other pendant group is fluorine, at least one othernon-hydrogen pendant group is present on said benzylidene component.Furthermore, a composition of the same type of thermoplastic comprisingat least one mono-acetal alditol of the structure:

wherein R is independently selected from hydrogen, lower alkyl groupscontaining 1-4 carbon atoms, lower alkoxy groups, chlorine, andfluorine; R₁ and R₂ are selected from lower alkyl groups containing 1-4carbon atoms, lower alkoxy groups, chlorine, and fluorine; with theproviso that one and only one of R₁ and R₂ is fluorine. Such monoacetalcompounds are also encompassed within this invention.

It should be appreciated with regard to the structural formula set forthabove that while only the 1,3:2,4 isomer is represented, this structureis provided for convenience only and the invention is not limited toonly isomers of the 1,3:2,4 type, but may include any and all otherisomers as well so long as the compound contains two aldehydesubstitutents on the alditol moiety.

The diacetals and monoacetals of the present invention are condensationproducts of alditol, such as sorbitol or xylitol, and a fluoro-alkylsubstituted benzaldehyde. Examples of suitable substituted benzaldehydesinclude 4-fluoro-3-methylbenzaldehyde, 3-fluoro-4-methylbenzaldehyde,4-fluoro-2,3-dimethylbenzaldehyde, 3-fluoro-2,4-dimethylbenzaldehyde,2,4-difluoro-3-methylbenzaldehyde, 4-fluoro-3,5-dimethylbenzaldehyde,and 3-fluoro-4-methoxybenzaldehyde. Preferred di-acetals of the presentinvention include bis(4-fluoro-3-methylbenzylidene)sorbitol andbis(3-fluoro-4-methylbenzylidene)sorbitol.

The compositions of the present invention also include solvent gelscontaining 0.2% to 10% of the above di-acetals as a gelling agent.Solvents useful herein include, as merely examples, lower monohydricalcohols, polyhydric alcohols, and mixtures thereof. Water may also beincluded as a portion of the solvent. However, the solvent willgenerally comprise water at levels no greater than 5% by weight of thefinal composition. Examples of solvents which may be utilized in thepresent invention include liquid polyethylene glycols (e.g., diethyleneglycol, triethylene glycol), liquid polypropylene glycols (e.g.,dipropylene glycol, tripropylene glycol), liquid polypropylenepolyethylene glycol copolymers, ethanol, n-propanol, n-butanol,t-butanol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol,1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol,1,2-butylene glycol, isopropanol, isobutanol, diethylene glycol,monomethyl ether, diethylene glycol, monoethylether, 1,3-butyleneglycol, 2,3-butylene glycol, 2,4-dihydroxy-2-methylpentane, trimethyleneglycol, glycerine, 1,3-butane diol, 1,4-butane diol, and the like, andmixtures thereof. As used herein, polyethylene glycols, polypropyleneglycols, and polypropylene polyethylene glycol copolymers include alkylether derivatives of these compounds (e.g., ethyl, propyl, and butylether derivatives). Examples of such compounds are butyl etherderivatives of polypropylene polyethylene glycol copolymers, such asPPG-5-buteth-7.

These solvents are fully described, for example, in U.S. Pat. No.4,518,582 to Schamper et al. and European Published Application 107,330to Luebbe et al. incorporated herein by reference. The preferredsolvents for use herein include liquid polyethylene glycols, liquidpolypropylene glycols, liquid polypropylene polyethylene glycolcopolymers, propylene glycol, 1,3-butylene glycol, and2,4-dihydroxy-2-methylpentane (sometimes referred to as hexyleneglycol), and mixtures thereof. Particularly preferred solvents includepropylene glycol, dipropylene glycol, tripropylene glycol, triethyleneglycol, hexylene gylcol, and mixtures thereof.

Other organic solvents useful herein include aromatics, halogenatedaromatics, nitrated aromatics, ketones, amines, nitriles, esters,aldehydes, and mixtures thereof. Examples of solvents which may beutilized in the present invention include xylenes (o, m, andp-substituted), 2-chlorotoluene, fluorobenzene, nitrobenzene,benzonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), and1-methyl-2-pyrrolidinone (NMP).

The di-acetals and monoacetals of the present invention may be preparedby a variety of techniques, some of which are known in the art.Generally, such procedures employ the reaction of one mole of D-sorbitolwith about 2 moles of aldehyde (for diacetals), with 1 mole of aldehydefor monoacetals, in the presence of an acid catalyst. The temperatureemployed in the reaction will vary widely depending upon thecharacteristics, such as melting point, of the aldehyde or aldehydesemployed as a starting material in the reaction. The reaction medium maybe an aqueous medium or a non-aqueous medium. One very advantageousmethod that can be employed to prepare di-acetals of the invention isdescribed in U.S. Pat. No. 3,721,682, to Murai et al. (New JapanChemical Company Limited), the disclosure of which is herebyincorporated herein by reference. While the disclosure of the patent islimited to benzylidene sorbitols, it has been found that the di-acetalsof the present invention may also be conveniently prepared by the methoddescribed therein. Additional methods for preparing DBS systems can befound in U.S. Pat. No. 5,731,474 to Scrivens et al., U.S. Pat. No.4,902,807 to Kobayashi et al. which discloses DBS having an alkyl groupor halogen for use as clarifying agents, and U.S. Pat. No. 5,106,999 toGardlik et al. which discloses the preparation ofdi(meta-fluorobenzylidene)sorbitol, di(meta-chlorobenzylidene)sorbitol,and di(meta-bromobenzylidene)sorbitol.

The inventive sorbitol di-acetals and monoacetals prepared by the abovetechniques may contain minor impurities (triacetals, for example).Although it may not always be necessary to remove these impurities(particularly if they are present in very low proportions) prior toincorporation of the di-acetal or monoacetal into the target polyolefin,it may be desirable to do so and such purification may serve to enhancethe transparency of the resin produced thereby. Purification of thedi-acetal may be accomplished, for instance, by removal of thetri-acetal impurities by the extraction thereof with a relativelynon-polar solvent. By removal of the impurities, the product may bepurified so that the amount of di-acetal in the additive compositioncontains at least about 90 percent and even up to 95 percent di-acetalor more.

The proportion of di-acetal or monoacetal in the composition of thisinvention is an amount sufficient to improve the transparency of thecomposition, generally from about 0.01 to about 2 percent by weight,preferably about 0.1 to about 1 percent by weight, based upon the totalweight of the composition may be provided. When the content of thedi-acetal is less than about 0.01 percent by weight, the resultingcomposition may not be sufficiently improved in respect to transparencycharacteristics. When the content of di-acetal or monoacetal isincreased beyond about 2 percent by weight, no additional advantage canbe observed.

The polyolefin polymers of the present invention may include aliphaticpolyolefins and copolymers made from at least one aliphatic olefin andone or more ethylenically unsaturated comonomers. Generally, thecomonomers, if present, constitute a minor amount, e.g., about 10percent or less or even about 5 percent or less, of the entirepolyolefin, based upon the total weight of the polyolefin. Suchcomonomers may serve to assist in clarity improvement of the polyolefin,or they may function to improve other properties of the polymer.Examples include acrylic acid and vinyl acetate, etc. Examples of olefinpolymers whose transparency can be improved conveniently according tothe present invention are polymers and copolymers of aliphaticmonoolefins containing 2 to about 6 carbon atoms which have an averagemolecular weight of from about 10,000 to about 2,000,000, preferablyfrom about 30,000 to about 300,000, such as polyethylene, linear lowdensity polyethylene, polypropylene, crystalline ethylenepropylenecopolymer, poly(1-butene), 1-hexene, 1-octene, vinyl cyclohexane, andpolymethylpentene. The polyolefins of the present invention may bedescribed as basically linear, regular polymers that may optionallycontain side chains such as are found, for instance, in conventional,low density polyethylene.

Other polymers that may benefit from the nucleation and clarificationproperties of the sorbitol acetals of the present invention includepolyethylene terephthalate, polybutylene terephthalate, and polyamides,among others.

The olefin polymer or copolymer used in the composition of the presentinvention is crystalline, and the diffraction of light caused by microcrystals contained in it is considered to be responsible for thedeterioration of the transparency of the polymer. It is thought that thedi-acetal functions in the composition to reduce the size of themicrocrystals thereby improving the transparency of the polymer.

The composition of the present invention can be obtained by adding aspecific amount of the di-acetal or monoacetal directly to the olefinpolymer or copolymer, and merely mixing them by an suitable means.Alternatively, a concentrate containing as much as about 20 percent byweight of the di-acetal in a polyolefin masterbatch may be prepared andbe subsequently mixed with the resin. Furthermore, the inventive alditolderivatives (and other additives) may be present in any type of standardpolyolefin additive form, including, without limitation, powder, prill,agglomerate, liquid suspension, and the like, particularly comprisingdispersion aids such as polyolefin (e.g., polyethylene) waxes, stearateesters of glycerin, montan waxes, mineral oil, and the like. Basically,any form may be exhibited by such a combination or composition includingsuch combination made from blending, agglomeration, compaction, and/orextrusion.

Other additives such as a transparent coloring agent or plasticizers(e.g., dioctyl phthalate, dibutyl phthalate, dioctyl sebacate, mineraloil, or dioctyl adipate), can be added to the composition of the presentinvention so long as they do not adversely affect the improvement oftransparency of the product. It has been found that plasticizers such asthose exemplified above may in fact aid in the improvement of thetransparency by the di-acetal.

With regard to other additives it may also be desirable to employ thedi-acetals or monoacetals disclosed above in combination with otherconventional additives having known transparency improving effects suchas, for instance, para-t-butylbenzoic acid, its salts, low molecularweight waxy polypropylene and the like. It may even be desirable toprovide the particular di-acetals or monoacetals of the presentinvention in the polyolefin composition in combination with thepreviously described dibenzylidene sorbitol additive disclosed in U.S.Pat. No. 4,016,118 to Hamada et al. In such applications, generally atleast about 10 percent, preferably about 25 percent, or even about 50percent or more of the clarity improving component will be the diacetalsof the present invention, with the remainder being comprised of otherknown clarifying agents, plasticizers, etc.

The compositions of the present invention may be obtained by adding thefluorinated and alkylated benzylidene sorbitol acetal to the polymer orcopolymer and merely mixing the resultant composition by any suitablemeans. The composition may then be processed and fabricated by anynumber of different techniques, including, without limitation, injectionmolding, injection blow molding, injection stretch blow molding,injection rotational molding, extrusion, extrusion blow molding, sheetextrusion, film extrusion, cast film extrusion, foam extrusion,thermoforming (such as into films, blown-films, biaxially orientedfilms), thin wall injection molding, and the like into a fabricatedarticle.

Other additives may also be used in the composition of the presentinvention, provided they do not interfere with the primary benefits ofthe invention. It may even be advantageous to premix these additives orsimilar structures with the nucleating agent in order to reduce itsmelting point and thereby enhance dispersion and distribution duringmelt processing. Of particular interest is the incorporation of theinventive symmetrical compound or compounds with, without limitation toany specific additive nucleators or clarifiers, selected amounts, forexample bis(3,4-dimethylbenzylidene)sorbitol (hereinafter DMDBS),bis(3,4-dichlorobenzylidene)sorbitol,bis(3,4-difluorobenzylidene)sorbitol,bis(3-chloro-4-fluorobenzylidene)sorbitol, andbis(4-chloro-3-fluorobenzylidene)sorbitol. As noted below, such acombination provides unexpected haze benefits within target polyolefin(e.g., polypropylene) plastic articles. Such additives are well known tothose skilled in the art, and include plasticizers, lubricants, catalystneutralizers, antioxidants, light stabilizers, colorants, othernucleating agents, and the like. Some of these additives may providefurther beneficial property enhancements, including improved aesthetics,easier processing, and improved stability to processing or end useconditions.

In particular, it is contemplated that certain organoleptic improvementadditives be added for the purpose of reducing the migration of degradedbenzaldehydes from reaching the surface of the desired article. The term“organoleptic improvement additive” is intended to encompass suchcompounds and formulations as antioxidants (to prevent degradation ofboth the polyolefin and possibly the target alditol derivatives presentwithin such polyolefin), acid neutralizers (to prevent the ability ofappreciable amounts of residual acids from attacking the alditolderivatives), and benzaldehyde scavengers (such as hydrazides,hydrazines, and the like, to prevent the migration of foul tasting andsmelling benzaldehydes to the target polyolefin surface). Such compoundsand formulations can be added in any amounts in order to provide suchorganoleptic improvements as needed. However, the amounts should notappreciably affect the haze results for the target polyolefin itself.Thus, lower amounts on the order of from about 20 ppm to about 2,000 ppmof the total polyolefin component are desired.

The compositions of the present invention are suitable as additives toimprove the clarity of packaging materials and container materials forcosmetics, food-stuffs, and the like, because they give film, sheet, andother fabricated articles having excellent transparency and physicalproperties.

PREFERRED EMBODIMENTS OF THE INVENTION

The following examples further illustrate the present invention but arenot to be construed as limiting the invention as defined in the claimsappended hereto. All parts and percents given in these examples are byweight unless otherwise indicated.

DBS Formation

Example 1 Preparation of Bis(4-fluoro-3-methylbenzylidene)sorbitol

A one liter four-necked cylindrical shaped reaction flask equipped witha Dean-Stark trap, condenser, thermometer, nitrogen inlet, and amechanical stirrer was charged with 40.55 g of sorbitol (0.2226 mole),600 mL of cyclohexane, 61.50 g of 4-fluoro-3-methylbenzaldehyde (0.4452moles), 2.90 g of p-toluenesulfonic acid, 2.4 mL of water, and 210 mL ofmethanol. The reaction was stirred and heated under reflux with removalof water through the Dean Stark trap. The reaction becomes very thickand additional solvent is added as needed. After about six hours, thereaction is cooled, neutralized with potassium hydroxide, and filtered.The wet cake was washed thoroughly with water and cyclohexane, dried ina vacuum oven at 110° C. to give 74.20 g ofBis(4-fluoro-3-methylbenzylidene)sorbitol (as determined throughInfrared Spectroscopy, Gas Chromatography/Mass Spectrometry, ¹H NMR, andC¹³ NMR, all collectively hereinafter referred to as “standardanalyses”). The purity was about 95% as determined by gas chromatography(GC). The melting point was determined to be [by Differential ScanningCalorimetry (DSC) @ 20° C./min] about 237.8° C.

Example 2 Preparation of Bis(3-fluoro-4-methylbenzylidene)sorbitol

A one liter four-necked cylindrical shaped reaction flask equipped witha Dean-Stark trap, condenser, thermometer, nitrogen inlet, and amechanical stirrer was charged with 42.00 g of sorbitol (0.2306 mole),600 mL of cyclohexane, 63.70 g of 3-fluoro-4-methylbenzaldehyde (0.4611moles), 3.00 g of p-toluenesulfonic acid, 2.5 mL of water, and 210 mL ofmethanol. The reaction was stirred and heated under reflux with removalof water through the Dean Stark trap. The reaction becomes very thickand additional solvent is added as needed. After about six hours, thereaction is cooled, neutralized with potassium hydroxide, and filtered.The wet cake was washed thoroughly with water and cyclohexane, dried ina vacuum oven at 110° C. to give 85.18 g ofBis(3-fluoro-4-methylbenzylidene)sorbitol (as determined throughstandard analyses). The purity was about 95% as determined by GC. Themelting point was determined to be (DSC @ 20° C./min) about 278.8° C.

Example 3 Preparation of Bis(4-fluoro-3-methylbenzylidene)xylitol

A one liter four-necked cylindrical shaped reaction flask equipped witha Dean-Stark trap, condenser, thermometer, nitrogen inlet, and amechanical stirrer was charged with 35.08 g of xylitol (0.2306 mole),600 mL of cyclohexane, 63.70 g of 4-fluoro-3-methylbenzaldehyde (0.4611moles), 3.00 g of p-toluenesulfonic acid, 2.5 mL of water, and 210 mL ofmethanol. The reaction was stirred and heated under reflux with removalof water through the Dean Stark trap. The reaction becomes very thickand additional solvent is added as needed. After about six hours, thereaction is cooled, neutralized with potassium hydroxide, and filtered.The wet cake was washed thoroughly with water and cyclohexane, dried ina vacuum oven at 110° C. to give 69.46 g ofBis(4-fluoro-3-methylbenzylidene)xylitol (as determined through standardanalyses). The purity was about 95% as determined by GC. The meltingpoint was determined to be (DSC @ 20° C./min) about 222.9° C.

Example 4 Preparation of 2,4-Mono(4-fluoro-3-methylbenzylidene)sorbitol

A two liter cylindrical shaped reaction flask equipped with a mechanicalstirrer was charged with 237.37 g of sorbitol (1.303 mole), 250 mL ofwater, 22.50 g of 4-fluoro-3-methylbenzaldehyde (0.1629 moles), 40 mL ofconcentrated HCI, and 0.20 g of dodecylbenzene sulfonate. The reactionmixture was then stirred for 14 h at 25° C. After neutralization with56.0 g of KOH, crude 2,4-Mono(4-fluoro-3-methylbenzylidene)sorbitol wasfiltered and collected. The crude product was recrystallized from waterseveral times to give 3.31 g of2,4-mono(4-fluoro-3-methylbenzylidene)sorbitol having the structure of:

(through standard analyses). The purity was about 98% as judged by GC.The melting point was measured (DSC @ 20° C./min) to be about 178.0° C.

Example 5 Preparation of Bis(4-chloro-3-fluorobenzylidene)sorbitol

A one liter four-necked cylindrical shaped reaction flask equipped witha Dean-Stark trap, condenser, thermometer, nitrogen inlet, and amechanical stirrer was charged with 42.00 g of sorbitol (0.2306 mole),600 mL of cyclohexane, 73.1 1 g of4-chloro-3-fluorobenzaldehyde (0.461 1moles), 3.00 g of p-toluenesulfonic acid, 2.5 mL of water, and 210 mL ofmethanol. The reaction was stirred and heated under reflux with removalof water through the Dean Stark trap. The reaction becomes very thickand additional solvent is added as needed. After about six hours, thereaction is cooled, neutralized with potassium hydroxide, and filtered.The wet cake is washed thoroughly with water and cyclohexane, dried in avacuum oven at 110° C. to give 93.02 g ofBis(4-chloro-3-fluorobenzylidene)sorbitol (as determined throughstandard analyses). The purity was about 95% as judged by GC. Themelting point was measured (DSC @ 20° C./min) to be about 262.0° C.

Example 6 Preparation of Bis(3-chloro-4-fluorobenzylidene)sorbitol

A one liter four-necked cylindrical shaped reaction flask equipped witha Dean-Stark trap, condenser, thermometer, nitrogen inlet, and amechanical stirrer was charged with 34.30 g of sorbitol (0.1883 mole),600 mL of cyclohexane, 59.70 g of 3-chloro-4-fluorobenzaldehyde (0.3765moles), 2.50 g of p-toluenesulfonic acid, 2.1 mL of water, and 210 mL ofmethanol. The reaction was stirred and heated under reflux with removalof water through the Dean Stark trap. The reaction becomes very thickand additional solvent is added as needed. After about six hours, thereaction is cooled, neutralized with potassium hydroxide, and filtered.The wet cake is washed thoroughly with water and cyclohexane, dried in avacuum oven at 110° C. to give 39.13 g ofBis(3-chloro-4-fluorobenzylidene)sorbitol (as determined throughstandard analyses). The purity was about 95% as judged by GC. Thecompound showed melting transitions (DSC @ 20° C./min) at 204.8 and220.0° C.

Polyolefin Formation and Testing

Thermoplastic compositions (plaques) and certain gels were producedcomprising a the additives from the EXAMPLEs above and sample randomcopolymer polypropylene (RCP) resins, polypropylene homopolymers (HP),Impact Copolymer (ICP), and Linear Low Density Polyethylene (LLDPE),produced dry blended in a Welex mixer at ˜2000 rpm, extruded through asingle screw extruder at 400-450° F., and pelletized. Accordingly, onekilogram batches of target polypropylene were produced in accordancewith the following table:

RANDOM COPOLYMER POLYPROPYLENE COMPOSITION TABLE Component AmountPolypropylene random copolymer flake (3% ethylene) 1000 g (MF = 12)Irganox ® 1010, Primary Antioxidant (from Ciba) 500 ppm Irgafos ® 168,Secondary Antioxidant (from Ciba) 1000 ppm Calcium Stearate, AcidScavenger 800 ppm Inventive Diacetal (and diacetal compositions) asnoted

The base resin (random copolymer, hereinafter “RCP”) and all additiveswere weighed and then blended in a Welex mixer for 1 minute at about1600 rpm. All samples were then melt compounded on a Killion singlescrew extruder at a ramped temperature from about 204° to 232° C.through four heating zones. The melt temperature upon exit of theextruder die was about 246° C. The screw had a diameter of 2.54 cm and alength/diameter ratio of 24:1. Upon melting the molten polymer wasfiltered through a 60 mesh (250 micron) screen. Plaques of the targetpolypropylene were then made through extrusion into an Arburg 25 toninjection molder. The molder molder was set at a temperature anywherebetween 190 and 260° C., with a range of 190 to 240° C. preferred, mostpreferably from about 200 to 230° C. (for the Tables below, the standardtemperature was 220; a # denotes a temperature 210, a {circumflex over(0)} denotes a temperature of 200, and a @ denotes a temperature of230). The plaques had dimensions of about 51 mm×76 mm×1.27 mm, and weremade in a mold having a mirror finish. The mold cooling circulatingwater was controlled at a temperature of about 25° C.

The same basic procedures were followed for the production of plaques ofHP and LLDPE plastics but with the following compositions:

HOMOPOLYMER POLYPROPYLENE COMPOSITION TABLE Component AmountPolypropylene homopolymer (MFI = 2)(Montell 630) 1000 g Irganox ® 1010,Primary Antioxidant (from Ciba) 500 ppm Irgafos ® 168, SecondaryAntioxidant (from Ciba) 1000 ppm Calcium Stearate, Acid Scavenger 800ppm Inventive Diacetal (and diacetal compositions) as noted

LINEAR LOW DENSITY POLYETHYLENE COMPOSITION TABLE Component AmountDowlex ® 2517 Linear Low Density Polyethylene (with 1000 g Antioxidantsand Acid scavengers already supplied) Sodium Stearate 500 ppm InventiveDiacetal (and diacetal compositions) as noted

The haze values were measured by ASTM Standard Test Method D1003-61“Standard Test Method for Haze and Luminous Transmittance of TransparentPlastics” using a BYK Gardner XL-211 Hazemeter. Nucleation capabilitieswere measured as polymer recrystallization temperatures (which indicatethe rate of polymer formation provided by the presence of the nucleatingadditive) by melting the target plaques, cooling the plaques at a rateof about 20° C./minute, and recording the temperature at which polymerre-formation occurs. Control plaques without alditol additives as wellas 3,4-dimethyldibenzylidene sorbitol (3,4-DMDBS) were produced forcomparative purposes for some or all of the above-noted measurements.Plaques of various thicknesses (50 mil, 100 mil, and 3 mm) were thenprepared by injection molding at 400-430° F. The haze values weremeasured by ASTM Standard Test Method D1003-61 “Haze and luminoustransmittance of transparent plastics” using a Gardner Hazemeter.Control plaques without alditol additives as well as3,4-dimethyldibenzylidene sorbitol (3,4-DMDBS),3,4-dimethyldibenzylidene xylitol 3,4-DMDBS), dibenzylidene sorbitol(DBS) alone, and NA-11 (a polyolefin nucleator available from AsahiDenka Co.) containing plaques, as noted below within the examples, wereproduced for comparative purposes for some or all of the above-notedmeasurements. An asterisk (*) denotes no measurements were taken.

TABLE 1 Additive - Part Polym. Ex. from Example Conc. Haze Resin Thick.Recryst. No. # above (%) (%) Grade (mil) Temp. 4 Control — 60.9 RCP 50 94.6 5 2 .15 16.9 RCP 50 * 6 2 .25  7.8 RCP 50 111.8 7 2 .35  7.2 RCP50 112.2 8 2 .50  7.0 RCP 50 *

TABLE 2 Additive - Part Polym. Ex. from Example Conc. Haze Resin Thick.Recryst. No. # above (%) (%) Grade (mil) Temp. 9 Control (#) — 59.8 RCP50  94.3 10 1 (#) .16 19.2 RCP 50 * 11 1 (#) .24  8.6 RCP 50 * 12 1 (#).30  7.1 RCP 50 114.1 13 1 (#) .40  6.8 RCP 50 114.3

TABLE 2 Additive - Part Polym. Ex. from Example Conc. Haze Resin Thick.Recryst. No. # above (%) (%) Grade (mil) Temp. 14 Control ({circumflexover ( )}) — 61.3 RCP 50  95.1 15 3 ({circumflex over ( )}) .15 55.6 RCP50 * 16 3 ({circumflex over ( )}) .25 49.1 RCP 50 * 17 3 ({circumflexover ( )}) .35 45.7 RCP 50 * 18 3 ({circumflex over ( )}) .50 38.0 RCP50 108.1 19 3,4-DMDBX({circumflex over ( )}) .50 25.0 RCP 50 109.4

TABLE 4 Part Ex. Additive - from Example Conc. Haze Resin Thick. No. #above (%) (%) Grade (mil) 20 Control — 90.7 RCP 100 21 1 .25 30.0 RCP100 22 1 .35 28.4 RCP 100 23 1 .45 27.2 RCP 100 24 5 (#) .12 26.1 RCP 50 25 5 (#) .16 12.4 RCP  50 26 5 (#) .24  8.0 RCP  50 27 5 (#) .30 7.6 RCP  50 28 5 (#) .40  7.3 RCP  50 29 6 .25 17.0 RCP  50 30 6 .3510.4 RCP  50 31 6 .50  8.3 RCP  50

TABLE 5 Additive - Part Polym. Ex. from Example Conc. Haze Resin Thick.Recryst. No. # above (%) (%) Grade (mil) Temp. 32 None (@) — 78.1 HP 50107.9 33 1 (@) .25 19.4 HP 50 121.9 34 1 (@) .35 11.5 HP 50 125.3 35 1(@) .50 10.0 HP 50 * 36 4 (@) .25 67.7 HP 50 110.3

TABLE 6 Additive - Part Polym. Flex Ex. from Example Conc. Resin Thick.Recryst. Mod. No. # above (%) Grade (mm) Temp. (MPa) 37 None (@) — ICP3.0 107.9 1005 38 1 (@) .20 ICP 3.0 115.2 1138 39 1 (@) .25 ICP 3.0121.3 1179 40 1 (@) .35 ICP 3.0 124.5 1207 41 NA-11 .10 ICP 3.0 122.81158

TABLE 7 Additive - Part Polym. Ex. from Example Conc. Haze Resin Thick.Recryst. No. # above (%) (%) Grade (mil) Temp. 42 None ({circumflex over( )}) — 93.9 LLDPE 50  99.0 43 1 ({circumflex over ( )}) .15 55.3 LLDPE50 * 44 1 ({circumflex over ( )}) .20 47.1 LLDPE 50 * 45 1 ({circumflexover ( )}) .25 47.6 LLDPE 50 108.1 46 1 ({circumflex over ( )}) .15 51.9LLDPE 50 * 47 1 ({circumflex over ( )}) .20 53.6 LLDPE 50 * 48 3,4-DMDBS({circumflex over ( )}) .25 53.6 LLDPE 50 108.3 49 DBS ({circumflex over( )}) .15 63.0 LLDPE 50 * 50 DBS ({circumflex over ( )}) .25 62.6 LLDPE50 106.1

Thus, the inventive fluoro-alkyl alditol derivatives provided similar,if not better, characteristics within the target thermoplastics ascompared with the control and other compositions comprising other typesof clarifying and/or nucleating additives.

Gel Formation Examples

Solid gels were also produced comprising the inventive alditolderivatives through recognized, simple methods. In particular, specificorganic solvents were combined with the additives in certainconcentrations and mixed thoroughly. The resultant mixture was thenheated to a temperature between about 170° F (77° C.) and 300° F. (149°C.), as indicated below, under agitation for between 5 and 120 minutes.The resultant solution was then poured into a mold to produce a gelstick. The solvents listed below are not intended to be exhaustive as tothe potential types which may be utilized to form gels with theinventive alditol derivatives, and thus are merely listed as preferredsolvents for such purposes. The examples below were analyzed empiricallyand by touch to determine if a gel actually formed and the hardnessproperties as well as any formed gels.

TABLE 8 Additive - DBS Gel from Conc. Forma- Gel Ex. Example (weighttion Character No. Solvent # above %) (Y/N) (Hard/Soft) 511,2-Propanediol 1 0.5 Y S 52 1,2-Propanediol 1 1 Y H 53 1,2-Propanediol1 2 Y H 54 1,2-Propanediol 1 3 Y H 55 1,2-Propanediol 1 5 Y H 561,3-Propanediol 1 0.5 N — 57 1,3-Propanediol 1 1 Y S 58 1,3-Propanediol1 2 Y H 59 1,3-Propanediol 1 3 Y H 60 1,3-Propanediol 1 5 Y H 61Triethylene Glycol 1 0.5 N — 62 Triethylene Glycol 1 1 N — 63Triethylene Glycol 1 2 Y H 64 Triethylene Glycol 1 3 Y H 65 TriethyleneGlycol 1 5 Y H 66 Poly(ethyleneglycol) 1 0.5 N S 67 Poly(ethyleneglycol)1 1 N S 68 Poly(ethyleneglycol) 1 2 Y H 69 Poly(ethyleneglycol) 1 3 Y H70 Poly(ethyleneglycol) 1 5 Y H 71 1-Butanol 1 0.5 Y S 72 1-Butanol 1 1Y S 73 1-Butanol 1 2 Y H 74 1-Butanol 1 3 Y H 75 1-Butanol 1 5 Y H 76Mineral Oil 1 0.5 Y S 77 Mineral Oil 1 1 Y S 78 Mineral Oil 1 2 Y S 79Mineral Oil 1 3 Y S 80 Mineral Oil 1 5 Y S 81 Xylene 1 0.5 Y S 82 Xylene1 1 Y S 83 Xylene 1 2 Y S 84 Xylene 1 3 Y S 85 Xylene 1 5 Y S 862-Chlorotoluene 1 0.5 Y S 87 2-Chlorotoluene 1 1 Y S 88 2-Chlorotoluene1 2 Y H 89 2-Chlorotoluene 1 3 Y H 90 2-Chlorotoluene 1 5 Y H

TABLE 9 Additive - DBS Gel from Conc. Forma- Gel Ex. Example (weighttion Character No. Solvent # above %) (Y/N) (Hard/Soft)  911,2-Propanediol 2 0.5 Y S  92 1,2-Propanediol 2 1 Y H  931,2-Propanediol 2 3 Y H  94 1,3-Propanediol 2 0.5 N —  951,3-Propanediol 2 1 Y H  96 1,3-Propanediol 2 3 Y H  97 1-Butanol 2 0.5Y S  98 1-Butanol 2 1 Y H  99 1-Butanol 2 3 Y H 100 2-Chlorotoluene 20.5 Y S 101 2-Chlorotoluene 2 1 Y S 102 2-Chlorotoluene 2 3 Y S 103Nitrobenzene 2 0.5 Y H 104 Nitrobenzene 2 1 Y H 105 Nitrobenzene 2 3 Y H106 Benzonitrile 2 0.5 Y S 107 Benzonitrile 2 1 Y H 108 Benzonitrile 2 3Y H

Thus, the inventive fluoro-alkyl alditol derivatives provide excellentgelling capabilities for solvents, depending on their concentrationwithout the target solvents.

Compositions with Other Clarifiers

Formulations of the inventive compound from Example I above were thenproduced incorporating other polyolefin clarifying benzylidenederivative compounds (such as DMDBS, etc., as listed in the Table below)in various proportions. RCP polypropylene was compounded as noted above(with lower molder barrel temperatures of about 200° C. marked with a #)but with mixtures-of such other clarifiers and the inventive compoundsof Example 1 into 50 mil and 100 mil plaques. Haze measurements weretaken as noted above as well. The other clarifier compounds added withinthe samples below are as follows:

A—DMDBS

B—Bis(3,4-dichlorobenzylidene)sorbitol

C—Bis(3,4-difluorobenzylidene)sorbitol

D—Bis(3-chloro-4-fluorobenzylidene)sorbitol

E—Bis(4-chloro-3-fluorobenzylidene)sorbitol

The haze results for such mixed formulations within target RCP plaquesare tabulated below:

TABLE 10 Physical Mixtures Inventive DBS Compounds And Other PolyolefinClarifiers Additive (Example # from above) mixed with other clarifiersPolym. Test (letter from Part Recryst. Plaque above) (plus ratio ofConc. Haze Resin Thick Temp. No. Additive to clarifier) (%) (%) Grade(mil) (° C.) 109 1 plus A [50/50] .2  7.3 RCP  50 * 110 1 plus A [50/50].25  6.6 RCP  50 * 111 1 plus A [50/50] .35  6.3 RCP  50 112.1 112 1plus A [50/50] .5  6.6 RCP  50 * 113 1 plus A [50/50] .15 33.5 RCP 100 *114 1 plus A [50/50] .2 22.4 RCP 100 * 115 1 plus A [50/50] .25 18.8 RCP100 112.1 116 1 plus A [50/50] .35 22.3 RCP 100 * 117 1 plus B [50/50] #.35  6.4 RCP  50 * 118 1 plus B [50/50] # .5  6.6 RCP  50 * 119 1 plus C[50/50] # .35  8.1 RCP  50 * 120 1 plus C [50/50] # .5  7.7 RCP  50 *121 1 plus D [50/50] # .35  8.0 RCP  50 * 122 1 plus D [50/50] # .5  6.9RCP  50 * 123 1 plus E [50/50] # .35  7.7 RCP  50 * 124 1 plus E [50/50]# .5  7.0 RCP  50 *

Thus, the inventive compound also exhibited excellent haze measurementsin polypropylene in the presence of another clarifying agent.

There are, of course, many alternative embodiments and modifications ofthe present invention which are to be included within the spirit andscope of the following claims.

What is claimed is:
 1. A solid gelled composition comprising: (a) about0.25% to about 10% of a gelling agent selected from at least onebenzylidene alditol acetal that has at least one substituted benzylidenecomponent having at least one fluorine pendant group and at least oneother pendant group, wherein said at least one other pendant group isnot hydrogen, and wherein if said at least one other pendant group isfluorine, at least one other non-hydrogen pendant group is present onsaid benzylidene component, and any mixtures thereof; and (b) from about10% to about 98%) of a solvent for said gelling agent.
 2. A solid gelaccording to claim 1 wherein the solvent is selected from the groupconsisting of monohydric alcohols, polyhydric alcohols, propylenecarbonate, propylene glycol, dipropylene glycol, DMSO, DMF, NMP, water,and mixtures thereof.
 3. A solid gel according to claim 2 wherein thesolvent is selected from the group consisting of propylene carbonate,methanol, ethanol, n-propanol, n-butanol, 2-methoxyethanol,2-ethoxyethanol, ethylene glycol, 1,2-propylene glycol, 1,3-propyleneglycol, 1,4-butylene glycol, 1,2-butylene glycol, diethylene glycol,isopropanol, isobutanol, monomethyl ether, diethylene glycol monoethylether, 1,3-butylene glycol, 2,3-butylene glycol, dipropylene glycol,2,4-dihydroxy-2-methylpentane, and mixtures thereof.
 4. A solid gelaccording to claim 2 wherein the solvent is selected from aromatics,halogenated aromatics, nitrated aromatics, ketones, amines, nitrites,esters, aldehydes, and mixtures thereof.
 5. A solid gelled compositioncomprising: (a) about 0.25% to about 10% of a gelling agent selectedfrom at least one benzylidene alditol acetal conforming to the structureof either structure (I) or (II)

wherein R is selected from hydrogen, lower alkyl groups containing 1-4carbon atoms, lower alkoxy groups, and fluorine; R₁, R₂, R₃, and R₄ areselected from lower alkyl groups containing 1-4 carbon atoms, loweralkoxy groups, and fluorine; with the proviso that only one of R₁ and R₂is fluorine, only one of R₃ and R₄ is fluorine, and wherein at least oneof R₁, R₂, R₃, and R₄ is a lower alkyl group; and (b) from about 10% toabout 98% of a solvent for said gelling agent.
 6. A solid gel accordingto claim 5 wherein the solvent is selected from the group consisting ofmonohydric alcohols, polyhydric alcohols, propylene carbonate, propyleneglycol, dipropylene glycol, DMSO, DMF, NMP, water, and mixtures thereof.7. A solid gel according to claim 5 wherein the solvent is selected fromthe group consisting of propylene carbonate, methanol, ethanol,n-propanol, n-butanol, 2-methoxyethanol, 2-ethoxyethanol, ethyleneglycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol,1,2-butylene glycol, diethylene glycol, isopropanol, isobutanol,monomethyl ether, diethylene glycol monoethyl ether, 1,3-butyleneglycol, 2,3-butylene glycol, dipropylene glycol,2,4-dihydroxy-2-methylpentane, and mixtures thereof.
 8. A solid gelaccording to claim 5 wherein the solvent is selected from aromatics,halogenated aromatics, nitrated aromatics, ketones, amines, nitriles,esters, aldehydes, and mixtures thereof.